CN1070363C - Substituted benzylidenecyanoacetic acid esters - Google Patents
Substituted benzylidenecyanoacetic acid esters Download PDFInfo
- Publication number
- CN1070363C CN1070363C CN96197766A CN96197766A CN1070363C CN 1070363 C CN1070363 C CN 1070363C CN 96197766 A CN96197766 A CN 96197766A CN 96197766 A CN96197766 A CN 96197766A CN 1070363 C CN1070363 C CN 1070363C
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- Prior art keywords
- chemical compound
- formula
- group
- acid esters
- tert
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
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- CDUQMGQIHYISOP-UHFFFAOYSA-N 2-cyano-3-phenylprop-2-enoic acid Chemical class OC(=O)C(C#N)=CC1=CC=CC=C1 CDUQMGQIHYISOP-UHFFFAOYSA-N 0.000 title 1
- 150000001875 compounds Chemical class 0.000 claims abstract description 26
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 claims abstract description 9
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 5
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 5
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 claims abstract description 3
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims abstract description 3
- 239000000203 mixture Substances 0.000 claims description 9
- 239000002537 cosmetic Substances 0.000 claims description 7
- 230000000475 sunscreen effect Effects 0.000 claims description 7
- 239000000516 sunscreening agent Substances 0.000 claims description 7
- 229910052799 carbon Inorganic materials 0.000 claims description 6
- 239000003795 chemical substances by application Substances 0.000 claims description 3
- 239000004611 light stabiliser Substances 0.000 claims description 3
- 125000004178 (C1-C4) alkyl group Chemical group 0.000 abstract 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 9
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 9
- 239000002253 acid Substances 0.000 description 7
- -1 sheet Substances 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- MLIREBYILWEBDM-UHFFFAOYSA-N cyanoacetic acid Chemical compound OC(=O)CC#N MLIREBYILWEBDM-UHFFFAOYSA-N 0.000 description 4
- 150000002148 esters Chemical class 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- DOZRDZLFLOODMB-UHFFFAOYSA-N 3,5-di-tert-Butyl-4-hydroxybenzaldehyde Chemical compound CC(C)(C)C1=CC(C=O)=CC(C(C)(C)C)=C1O DOZRDZLFLOODMB-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N ethyl acetate Substances CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 150000003053 piperidines Chemical class 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- 238000013019 agitation Methods 0.000 description 2
- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzaldehyde Chemical compound O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 description 2
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 2
- 238000009833 condensation Methods 0.000 description 2
- 230000005494 condensation Effects 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 239000000499 gel Substances 0.000 description 2
- 239000006210 lotion Substances 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- 239000010409 thin film Substances 0.000 description 2
- LTMRRSWNXVJMBA-UHFFFAOYSA-L 2,2-diethylpropanedioate Chemical compound CCC(CC)(C([O-])=O)C([O-])=O LTMRRSWNXVJMBA-UHFFFAOYSA-L 0.000 description 1
- MLIREBYILWEBDM-UHFFFAOYSA-M 2-cyanoacetate Chemical compound [O-]C(=O)CC#N MLIREBYILWEBDM-UHFFFAOYSA-M 0.000 description 1
- 239000005711 Benzoic acid Substances 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 238000006000 Knoevenagel condensation reaction Methods 0.000 description 1
- OLXSZDSSDNKATC-UHFFFAOYSA-N N(=O)OC(C)CCCCCC.C(#N)CC(=O)O Chemical class N(=O)OC(C)CCCCCC.C(#N)CC(=O)O OLXSZDSSDNKATC-UHFFFAOYSA-N 0.000 description 1
- YBGZDTIWKVFICR-JLHYYAGUSA-N Octyl 4-methoxycinnamic acid Chemical compound CCCCC(CC)COC(=O)\C=C\C1=CC=C(OC)C=C1 YBGZDTIWKVFICR-JLHYYAGUSA-N 0.000 description 1
- 230000002159 abnormal effect Effects 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- XNEFYCZVKIDDMS-UHFFFAOYSA-N avobenzone Chemical compound C1=CC(OC)=CC=C1C(=O)CC(=O)C1=CC=C(C(C)(C)C)C=C1 XNEFYCZVKIDDMS-UHFFFAOYSA-N 0.000 description 1
- 150000003935 benzaldehydes Chemical class 0.000 description 1
- 235000010233 benzoic acid Nutrition 0.000 description 1
- 230000008033 biological extinction Effects 0.000 description 1
- JYYOBHFYCIDXHH-UHFFFAOYSA-N carbonic acid;hydrate Chemical compound O.OC(O)=O JYYOBHFYCIDXHH-UHFFFAOYSA-N 0.000 description 1
- 239000008294 cold cream Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000008271 cosmetic emulsion Substances 0.000 description 1
- 239000012043 crude product Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 229940126534 drug product Drugs 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 208000021302 gastroesophageal reflux disease Diseases 0.000 description 1
- 238000000265 homogenisation Methods 0.000 description 1
- 235000015110 jellies Nutrition 0.000 description 1
- 239000008274 jelly Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 description 1
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 description 1
- 125000001400 nonyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- WQDGUYZIAJKLAB-UHFFFAOYSA-N octan-2-yl nitrite Chemical compound CCCCCCC(C)ON=O WQDGUYZIAJKLAB-UHFFFAOYSA-N 0.000 description 1
- 229960001679 octinoxate Drugs 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- QNGNSVIICDLXHT-UHFFFAOYSA-N para-ethylbenzaldehyde Natural products CCC1=CC=C(C=O)C=C1 QNGNSVIICDLXHT-UHFFFAOYSA-N 0.000 description 1
- 239000000825 pharmaceutical preparation Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 230000035943 smell Effects 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 235000013599 spices Nutrition 0.000 description 1
- 230000004936 stimulating effect Effects 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 230000037072 sun protection Effects 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
Classifications
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
- A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
- A61K8/40—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing nitrogen
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61P—SPECIFIC THERAPEUTIC ACTIVITY OF CHEMICAL COMPOUNDS OR MEDICINAL PREPARATIONS
- A61P17/00—Drugs for dermatological disorders
- A61P17/16—Emollients or protectives, e.g. against radiation
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
- A61Q1/00—Make-up preparations; Body powders; Preparations for removing make-up
- A61Q1/02—Preparations containing skin colorants, e.g. pigments
- A61Q1/04—Preparations containing skin colorants, e.g. pigments for lips
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
- A61Q17/00—Barrier preparations; Preparations brought into direct contact with the skin for affording protection against external influences, e.g. sunlight, X-rays or other harmful rays, corrosive materials, bacteria or insect stings
- A61Q17/04—Topical preparations for affording protection against sunlight or other radiation; Topical sun tanning preparations
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C255/00—Carboxylic acid nitriles
- C07C255/01—Carboxylic acid nitriles having cyano groups bound to acyclic carbon atoms
- C07C255/32—Carboxylic acid nitriles having cyano groups bound to acyclic carbon atoms having cyano groups bound to acyclic carbon atoms of a carbon skeleton containing at least one six-membered aromatic ring
- C07C255/41—Carboxylic acid nitriles having cyano groups bound to acyclic carbon atoms having cyano groups bound to acyclic carbon atoms of a carbon skeleton containing at least one six-membered aromatic ring the carbon skeleton being further substituted by carboxyl groups, other than cyano groups
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K15/00—Anti-oxidant compositions; Compositions inhibiting chemical change
- C09K15/04—Anti-oxidant compositions; Compositions inhibiting chemical change containing organic compounds
- C09K15/20—Anti-oxidant compositions; Compositions inhibiting chemical change containing organic compounds containing nitrogen and oxygen
- C09K15/24—Anti-oxidant compositions; Compositions inhibiting chemical change containing organic compounds containing nitrogen and oxygen containing a phenol or quinone moiety
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2601/00—Systems containing only non-condensed rings
- C07C2601/12—Systems containing only non-condensed rings with a six-membered ring
- C07C2601/14—The ring being saturated
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- Health & Medical Sciences (AREA)
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Veterinary Medicine (AREA)
- General Health & Medical Sciences (AREA)
- Animal Behavior & Ethology (AREA)
- Public Health (AREA)
- Dermatology (AREA)
- Engineering & Computer Science (AREA)
- Birds (AREA)
- Epidemiology (AREA)
- Materials Engineering (AREA)
- Bioinformatics & Cheminformatics (AREA)
- Pharmacology & Pharmacy (AREA)
- Nuclear Medicine, Radiotherapy & Molecular Imaging (AREA)
- Medicinal Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Toxicology (AREA)
- Cosmetics (AREA)
Abstract
The invention concerns compounds of the formula I in which R<1> is isopropyl, isobutyl or t-butyl and R<2> is alkyl with 6-14 C-atoms, wherein R<3> being H or C1-C4 alkyl and m and n being 0 or 1.
Description
The present invention relates to the replacement benzylidenecyanoacetacid acid esters of formula I, this compounds is as the purposes of sunscreen, the application in cosmetics, and the cosmetic composition that contains these chemical compounds,
Sunscreen based on the benzylidenecyanoacetacid acid esters that replaces is known.BE 757036 has described the following formula: compound as the photaesthesia stimulative substance especially
DE 1087902 has described benzaldehyde and the condensation substance that contains the chemical compound of active methylene group.In many other chemical compounds, what can also mention is 4-hydroxyl-3, the condensation substance of 5-di-t-butyl benzaldehyde and diethyl malonate, cyan-acetic ester, Cyanoacetyl-Cyacetazid or malonic acid (page 1 the 2nd hurdle, VI group).These materials are as the light stabilizer of thin film, sheet, fiber and silk.
DE 2816819 has described the replacement benzylidenecyanoacetacid acid esters as the following structure of UV-A lightscreening agent:
It is found that for replacement situation possible on the aromatic ring, the best is para-position one replacement, and has optimal properties when substituent group is methoxyl group.For radicals R, find R=n-hexyl wherein, n-octyl, positive decyl, different nonyl and isodecyl chemical compound be best suited for.
Because the cosmetic sunscreen is except having for example suitable obtained the maximum absorption of optical property, high specific extinction and light stability, also have for example good oil-soluble of many other application features, pH stability, oxidation stability, heat stability, minimum intrinsic colour and itself do not have bad abnormal smells from the patient, but also must be that the toxicity aspect is acceptable.The objective of the invention is to make foregoing product in above-mentioned properties optimization.
The inventor finds that the formula I chemical compound has reached above-mentioned purpose, aspect above-mentioned needs many, particularly have the better character that is better than the prior art chemical compound aspect the light stability,
Wherein
R
1Be isopropyl, isobutyl group or the tert-butyl group,
R
2Be alkyl with 6-14 carbon atom,
R wherein
3=H or C
1-C
4-alkyl
And m, n=0 or 1.
In the formula I chemical compound, particularly suitable sunscreen is two R wherein
1All be the tert-butyl group and R
2Be have 8-12 carbon atom branched alkyl or-C
2H
4-C
6H
5Or
The formula I chemical compound.In addition, R
2Can be for example following group:
Particularly preferably be wherein R
1All be the tert-butyl group and R
2Be the formula I chemical compound of following formula group,
Can adopt Knoevenagel condensation reaction (referring to for example Organikum, 1988 editions, the 459th page), in a usual manner, prepare The compounds of this invention by corresponding benzaldehyde class and cyanoacetate.Can be according to conventional method, by with suitable alcohol with commercially available cyan-acetic ester transesterificationization, prepare corresponding cyan-acetic ester.
The compounds of this invention be particularly suitable for as with the light stabilizer of ultraviolet contact material, the described material that contacts with ultraviolet is for example silk, fiber, sheet, thin film and other moulded goods.
The compounds of this invention is particularly useful for protecting human body skin with pre-anti-ultraviolet.These chemical compounds can be widely used in cosmetics and drug products, for example suntan lotion, sunscreen, sunlight lotion, sun protection gel, lip pomade, cold cream, hair jelly and non-oil gel.
Embodiment
Embodiment 13,5-di-t-butyl-4-hydroxyl benzylidenecyanoacetacid acid 2-phenyl chlorocarbonate
With 5.9 grams 3,5-di-t-butyl-4-hydroxy benzaldehyde is dissolved in 50 milliliters of toluene.
With 4.7 gram cyanoacetic acid 2-phenyl chlorocarbonates, 0.1 gram piperidines and 0.25 gram acetic acid reflux.Remove 0.4 gram water with 2 hours azeotropic.With this mixture cooling, water and sodium bicarbonate solution washing, dry and concentrated.With the crude product recrystallization.Output: 9.9 grams (98%).
Embodiment 23,5-di-t-butyl-4-hydroxyl benzylidenecyanoacetacid acid 2-Octyl Nitrite
With 28.1 grams 3,5-di-t-butyl-4-hydroxy benzaldehyde is dissolved in 60 milliliters of toluene.Add 21.7 gram cyanoacetic acid 2-Octyl Nitrites, 0.27 gram piperidines and 0.67 gram acetic acid.This mixture heated is refluxed, and azeotropic is removed about 2 gram water.The washing clear solutions, dry and concentrated.Output: 46.2 gram light yellow oils (93%).
Embodiment 33,5-di-t-butyl-4-hydroxyl benzylidenecyanoacetacid acid 4-tert-butyl group cyclohexyl
With 5.4 grams 3,5-di-t-butyl-4-hydroxy benzaldehyde is dissolved in 50 milliliters of toluene.Add 5.9 gram cyanoacetic acid 4-tert-butyl group cyclohexyls, 0.1 gram piperidines and 0.25 gram acetic acid.Under refluxing, azeotropic is removed 0.4 gram water.With this mixture washing, dry and concentrated.Output: 10.6 gram crystallizations (96%).Character:
| Embodiment | λ max [nm] | E 1A | Dissolubility | Light stability |
| 1 | 356 | 484 | Good | 98％ |
| 2 | 357 | 638 | Fine | 99％ |
| 3 | 355 | 623 | Good | 92％ |
In room temperature, by above-mentioned substance being dissolved in benzoic acid C
12-C
15In-the Arrcostab, measure its dissolubility.
Solution by shining suitable chemical compound with Beraus Sun experimental provision 30 minutes is measured its light stability.The amount of residue chemical compound is represented with the percent of primary quantity.Comparing embodiment 1
Comparing embodiment 2
Parsol 1789 is commercially available prod (UV-A lightscreening agent) of permission.
Obviously, with the known compound of similar with compare with the commercially available prod of permission, The compounds of this invention has shown beat all advantage, particularly aspect important light stability.Purposes embodiment
Wherein can use the cosmetic composition of The compounds of this invention as described below with certain benefits.The conventional method of preparation cosmetic Emulsion:
In the container that is stirring, all oil-soluble compositions are heated to 85 ℃.
When all the components fusion and when being liquid phase, mix water and homogenize.
Under agitation; 40 ℃ of of of of emulsion is cooled to about; Adds spice; make this mixture homogenization then, and under agitation be cooled to 25 ℃.100 Eucerinum anhydricum10.00 10.00 0.5-10 18.00 5.00 4.00 4.00 ///[sic] ( pentaeryhrithyl ) 3.00 SE2.00 2.00 2.00 Quaternium-181.50 PEG-45/ ( micropigments ) 100 10.00 Parsol MCX6.00 PEG-7-6.00 0.5-10 15.00 5.00 5.00 3.00 3.00 4-2.00 PEG-45/1.00 1.00 0.50 PEG-40-0.50 0.50 0.20 EDTA100 8.00 7.00 0.5-10 25.00 5.00 PEG-25 PABA1.00 4-0.40 C10-C
300.30 0.25 0.25 0.20 EDTA0.15 0.15 0.10 ( SPF20 ) 100 8.00 8.00 6.00 PEG-7-0.5-10 26.00 5.00 5.00 5.00 3.00 2.00 PEG-45/1.00 4-0.60 0.50 0.25 0.20 EDTA0.15 ( ) 100 8.00 5.00 PEG-7-5.00 4.00 4.00 /0.5-10 24.00 3.00 2.00 4-2.00 1.50 PEG-45/1.50 0.70 0.50 0.15 ( SPF6 ) 100 10.00 6.00 PEG-7-5.00 3.50 0.5-10 23.00 /3.00 2.00 PEG-45/0.70 0.60 0.50 0.30 0.25 0.15 0.05
Claims (6)
1. formula I chemical compound
R wherein
1Be isopropyl, isobutyl group or the tert-butyl group, R
2Be alkyl with 6-14 carbon atom,
R wherein
3=H or C
1-C
4-alkyl and m, n=0 or 1.
2. the formula I chemical compound of claim 1, wherein R
1Be the tert-butyl group, and R
2Be have 8-12 carbon atom branched alkyl or-C
2H
4-C
6H
5Or
3. formula 1 chemical compound of claim 1, wherein R
1Be the tert-butyl group, and R
2It is the following formula group
Or
-CH
2-CH
2-C
6H
5
4. the chemical compound of claim 1 is as the purposes of sunscreen or light stabilizer.
5. the application of the chemical compound of claim 1 in cosmetics.
6. cosmetic composition, wherein the chemical compound that only contains claim 1 perhaps contains other UV-A or UV-B lightscreening agent simultaneously as sunscreen.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19539189A DE19539189A1 (en) | 1995-10-20 | 1995-10-20 | Substituted Benzylidencyanessigester |
| DE19539189.6 | 1995-10-20 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1200027A CN1200027A (en) | 1998-11-25 |
| CN1070363C true CN1070363C (en) | 2001-09-05 |
Family
ID=7775409
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN96197766A Expired - Fee Related CN1070363C (en) | 1995-10-20 | 1996-10-11 | Substituted benzylidenecyanoacetic acid esters |
Country Status (8)
| Country | Link |
|---|---|
| US (1) | US5935563A (en) |
| EP (1) | EP0857058B1 (en) |
| JP (1) | JPH11514371A (en) |
| CN (1) | CN1070363C (en) |
| AU (1) | AU713802B2 (en) |
| CA (1) | CA2231626A1 (en) |
| DE (2) | DE19539189A1 (en) |
| WO (1) | WO1997015279A1 (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1323192A (en) | 1998-10-16 | 2001-11-21 | 宝洁公司 | UV protection composition |
| DE19926779A1 (en) * | 1999-06-11 | 2000-12-14 | Basf Ag | Use of substituted vinyl tetrahydronaphthalenes and vinyl benzotetrahydropyrans as light stabilizers |
| US6180813B1 (en) * | 1999-06-11 | 2001-01-30 | Lord Corporation | Benzylidenecyanoacetates and a method for making benzylidenecyanoacetates |
| EP1407756B2 (en) * | 2002-09-13 | 2016-09-28 | Kao Corporation | Hair dye composition comprising methine dye |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE1443920A1 (en) * | 1961-03-29 | 1969-11-27 | Gen Aniline & Film Corp | New alpha-cyanocinnamic acid derivatives and their use as ultraviolet absorbers for organic substances |
| EP0005182A1 (en) * | 1978-04-18 | 1979-11-14 | Bayer Ag | Composition against the action of light |
| EP0192237A1 (en) * | 1985-02-19 | 1986-08-27 | Utah State University Foundation | Process for the degradation of enviromentally persistent organic compounds |
| DE4104624C1 (en) * | 1991-02-15 | 1993-01-21 | Reko Gmbh Entsorgung Und Recycling, 7123 Sachsenheim, De | Degradation of harmful organic material - using lignin-degrading organisms, without the need for specially prepd. substrate |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| BE396934A (en) * | 1933-06-15 | |||
| DE1087902B (en) * | 1956-06-19 | 1960-08-25 | Bayer Ag | Ultraviolet protective filter paste or layer |
| BE757036A (en) * | 1969-10-07 | 1971-03-16 | Fuji Photo Film Co Ltd | PHOTOSENSITIVE COLOR PHOTOGRAPHY MATERIALS WITH BETTER SOLIDITY TO LIGHT |
-
1995
- 1995-10-20 DE DE19539189A patent/DE19539189A1/en not_active Withdrawn
-
1996
- 1996-10-11 AU AU72900/96A patent/AU713802B2/en not_active Ceased
- 1996-10-11 CN CN96197766A patent/CN1070363C/en not_active Expired - Fee Related
- 1996-10-11 JP JP9516239A patent/JPH11514371A/en not_active Withdrawn
- 1996-10-11 EP EP96934630A patent/EP0857058B1/en not_active Expired - Lifetime
- 1996-10-11 US US09/051,898 patent/US5935563A/en not_active Expired - Fee Related
- 1996-10-11 WO PCT/EP1996/004417 patent/WO1997015279A1/en active IP Right Grant
- 1996-10-11 CA CA002231626A patent/CA2231626A1/en not_active Abandoned
- 1996-10-11 DE DE59607732T patent/DE59607732D1/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE1443920A1 (en) * | 1961-03-29 | 1969-11-27 | Gen Aniline & Film Corp | New alpha-cyanocinnamic acid derivatives and their use as ultraviolet absorbers for organic substances |
| EP0005182A1 (en) * | 1978-04-18 | 1979-11-14 | Bayer Ag | Composition against the action of light |
| EP0192237A1 (en) * | 1985-02-19 | 1986-08-27 | Utah State University Foundation | Process for the degradation of enviromentally persistent organic compounds |
| DE4104624C1 (en) * | 1991-02-15 | 1993-01-21 | Reko Gmbh Entsorgung Und Recycling, 7123 Sachsenheim, De | Degradation of harmful organic material - using lignin-degrading organisms, without the need for specially prepd. substrate |
Also Published As
| Publication number | Publication date |
|---|---|
| DE19539189A1 (en) | 1997-04-24 |
| AU713802B2 (en) | 1999-12-09 |
| JPH11514371A (en) | 1999-12-07 |
| WO1997015279A1 (en) | 1997-05-01 |
| DE59607732D1 (en) | 2001-10-25 |
| CN1200027A (en) | 1998-11-25 |
| US5935563A (en) | 1999-08-10 |
| EP0857058B1 (en) | 2001-09-19 |
| CA2231626A1 (en) | 1997-05-01 |
| AU7290096A (en) | 1997-05-15 |
| EP0857058A1 (en) | 1998-08-12 |
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